P
US9879039B2ActiveUtilityPatentIndex 98

Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues

Assignee: UNIV ARIZONA STATEPriority: Jun 3, 2015Filed: May 31, 2016Granted: Jan 30, 2018
Est. expiryJun 3, 2035(~8.9 yrs left)· nominal 20-yr term from priority
Inventors:LI JIANLI GUIJIE
H01L 51/0084C09K 11/06H01L 51/5016C09K 2211/1029H01L 51/0085C07F 15/006H01L 2251/5376C07F 15/0033C07F 15/0086H01L 51/0094H01L 51/0087C09K 2211/185C09K 2211/1044C09K 2211/1007Y02E10/549H10K 2101/27H10K 85/341H10K 50/11H10K 85/40H10K 85/346H10K 85/342H10K 2101/10
98
PatentIndex Score
83
Cited by
279
References
20
Claims

Abstract

Tetradentate and octahedral metal complexes suitable for use as phosphorescent or delayed fluorescent and phosphorescent emitters in display and lighting applications.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A complex of Formula AIV: 
       
         
           
           
               
               
           
         
         wherein: 
         M is Pt or Pd, 
         V 1  and V 4  are N, 
         V 2  and V 3  are C, 
         L 1  and L 4  are pyridyl; 
         L 2  and L 3  are phenyl; 
         each of A 1 , A 2 , A 3 , and A 4  is independently a single bond, CR 1 R 2 , C═O, SiR 1 R 2 , GeR 1 R 2 , NR 3 , PR 3 , R 3 P═O, AsR 3 , R 3 As═O, O, S, S═O, SO 2 , Se, Se═O, SeO 2 , BR 3 , R 3 Bi═O, or BiR 3 , 
         A 5  is O, NR 3 , CR 1 R 2 , or C═O, 
         X 1  and X 2  are N, 
         each of R a , R b , R c , and R d  is independently present or absent, and if present each of R a , R b , R c , and R d  is independently a mono-, di-, or tri-substitution as valency permits, and each of R a , R b , R c , and R d  is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof, 
         each of R x  and R y  is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination, and 
         each of R 1 , R 2  and R 3  is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof; wherein le and le are optionally linked together. 
       
     
     
       2. The complex of  claim 1 , wherein the complex has a neutral charge. 
     
     
       3. A complex represented by one of the chemical structures: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein M is Pt or Pd, and 
         each of R, R 1 , R 2 , R 3 , R 4 , R 5  and R 6  is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof. 
       
     
     
       4. The complex of  claim 1 , wherein each of 
       
         
           
           
               
               
           
         
       
       is independently one of the following structures: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein each of R 1 , R 2 , R 3  and R 4  is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric; or any conjugate or combination thereof. 
       
     
     
       5. An emitter comprising the complex of  claim 3 . 
     
     
       6. An emitter comprising the complex of  claim 1 , wherein the emitter is a delayed fluorescent and phosphorescent emitter. 
     
     
       7. An emitter comprising the complex of  claim 1 , wherein the emitter is a phosphorescent emitter. 
     
     
       8. An emitter comprising the complex of  claim 1 , wherein the emitter is a delayed fluorescent emitter. 
     
     
       9. The complex of  claim 1 , wherein polymeric comprises polyalkylene, polyester, or polyether. 
     
     
       10. The complex of  claim 9 , wherein polymeric comprises —(CH 2 O) n —CH 3 , —(CH 2 CH 2 O) n —CH 3 , —[CH 2 CH(CH 3 )] n —CH 3 , —[CH 2 CH(COOCH 3 )] n —CH 3 , —[CH 2 CH(COOCH 2 CH 3 )] n —CH 3 , or —[CH 2 CH(COO t Bu)] n —CH 3 , where n is an integer. 
     
     
       11. A device comprising a complex of  claim 1 . 
     
     
       12. The complex of  claim 1 , wherein each of A 1 , A 2 , A 3 , and A 4  is independently a single bond, CR 1 R 2 , C═O, SiR 1 R 2 , NR 3 , O, S, S═O, or SO 2 . 
     
     
       13. The complex of  claim 1 , wherein each of A 1 , A 2 , A 3 , and A 4  is independently a single bond, CR 1 R 2 , NR 3 , or O. 
     
     
       14. The complex of  claim 1 , wherein each of A 1 , A 2 , A 3 , and A 4  is independently a single bond or CR 1 R 2 . 
     
     
       15. The complex of  claim 1 , wherein A 5  is O, NR 3 , or CR 1 R 2 . 
     
     
       16. The complex of  claim 1 , wherein A 5  is O. 
     
     
       17. The complex of  claim 1 , wherein each R 1 , R 2  and R 3  is independently hydrogen, deuterium, halogen, hydroxyl; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, alkoxy, aryloxy, or haloalkyl. 
     
     
       18. The complex of  claim 1 , wherein each R 1 , R 2  and R 3  is independently hydrogen; substituted or unsubstituted: aryl, alkyl, alkenyl, or alkynyl. 
     
     
       19. The complex of  claim 1 , wherein each of R a , R b , R c , and R d  is independently present or absent, and if present each of R a , R b , R c , and R d  is independently a mono-, di-, or tri-substitution as valency permits, and each of R a , R b , R c , and R d  is independently hydrogen, halogen, hydroxyl; substituted or unsubstituted: aryl, heteroaryl, alkyl, alkenyl, or alkynyl, and
 each of R x  and R y  is independently hydrogen, halogen, hydroxyl; substituted or unsubstituted: aryl, heteroaryl, alkyl, alkenyl, or alkynyl. 
 
     
     
       20. The complex of  claim 1 , wherein the complex is

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